Poly (acrylonitrile-co-vinyl acetate)/polypyrrole composite particles with uniform size and morphology have been synthesized using one-step polymerization that involves swelling and coating of polypyrrole (PPy) into P (AN-co-VAc) latex nanoparticles. As an initial stage, free radical copolymerization of acrylonitrile (AN) and vinyl acetate (VAc) was synthesized by emulsion polymerization using ammonium persulfate (APS) and dodecyl benzene sulfonic acid salt (DBSA) as a surfactant. P (AN-co-VAc)/PPy composites were obtained first time by in situ addition of the pyrrole into the reaction medium. The electrospun P (AN-co-VAc)/PPy nanofibers were obtained from the nanoparticles with better properties and the effect of PPy on the morphology of nanofibers was studied by scanning electron microscopy (SEM). High degree of homogeneity and molecular order induced by molecular dispersion of polypyrrole on copolymer matrix without phase separation improve the transport properties and stability of polypyrrole, which are critical for high-performance organic electronics.